Method of modifying resin and the product thereof



f Modifying Resin and the Product I ammoniate as hereto ble of indefinite extension or dilution in jects, as for instance UNITED STATES PATENT- OFFICE.

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Specification of Letters intent. Patented 'D 27 1921 10 Draw ng. Original application filed January 10, 1919, semi at. 270,605. "Divided and this a ji;

catlon-flledl'anuaryfi, 1920. Serial No. 349,997.

Toell wlwm 'it may concerm V Beit. known that I GEORGE WI MILES, a citizen-ofthe United tates, and resident of Sandwich, in the county of Barnstable and 5 State: ofMassachusetts, have invented new and useful. Improvements in Methods of is a specification.

of which the following invention cons sts in a method of -10 modlfying resin by oxidation and in the oxidized resin which is the product'of the method. An object of the invention is to produce a form of resin capable of forming a resm-ammoma soatp wh1ch,unl1keres1nore produced, is" capes water. The ammoniate of my new oxidized resin constitutes a: water resistant coating 'materiahapplicable to a miscellany-of obpaper. The method of preparing theo'xidized resin ammoniate, and q the ammoniate itself, forms the subject mat-.

ter of my ap lication for United States Letters Patent, erial No. 270,605, filed January 10 1919 of which this'caseis a division. '1 v in or er to become. capable of forming an indefinitel extensible ammoniate, resin must be quite thoroughly oxidized, and so far as I am informed, such oxidation of'resin-as 30 may heretofore have taken p ace' by exposure to air has been, at, the utmost, a superficial reaction, afl 'ecting only a, .minor part of the" resin, even though it has been in comminuted condition. Oxi ation of resin by simple exposur'e'to air will not proceed to anything approaching adequate modification of the whole body ,of'resin, unless, addition to comminution; the resin-be repeatedly agitated in contact with air, over a period of 40Inonths. 1

' I have discovered three modes of oxidizing resin with that degree of thoroughness which is requisit to the obtainment of, a'. resin ca-,

pable of ormingan indefinitely extensible 45. or soluble ammoniate; these modes are exem lified b the following; I c

- 'nd or inary I'OSlIl to a very fine powsible to the air, and re eatedly stir it, so' to expose all the partlc es, and also, so as to separate portions which have oxidized" from the underlying unoxidized parts of the pars ticlesfthus exposing fresh surfaces to the ac-. "tion of oxygenin the air. If thIS PIQCe S S lSQ protracted for a long time, tfor weeks or T hereof,

months, the comminuted rosin will eventu-- ally become oxidized to that degree of thor:

,oughness which is requisite to formation of an indefinitely extensible rosimammonia soap. Heating the rosin will assistthe operation. The length of time required cannot be stated with accuracy; when the rosin yields by sample a clear fluid solution in an equal we1ght of water, which contains that quantity of ammonia requisite tosaponify' the resin, and this solution proves capable of indefinite extension, the indication is that the oxidation has proceeded to com letion'.

The foregoing method of oxi ation is" however, so 1 borious and uncertain, that do not recommend it, if either of the/other methods I have discovered, is available.

One of these, which like that ef exposure to airis one of simp e or unprovoked oxidation,;is to subject finely powdered rosin to the action of 'a strong solution of hydrogen peroxid. Stirring the rosin in the peroxid solution acceleratesithe oxidation, which becomes complete (as indicated by. the same 'test as above described) in a much shorter time than is necessary'when the simple .air-

exposure methodxis employed.-

explanatio'n of thiS -which I advance tentativelyis that H the solution of hydrogen peroxid 1 bri" the oxygen into a more intimate contact with the rosin thaif is possible in dry air, I and that agitation of the resin during treatment loosens the oxidized portions, as they are formed, from portions remain'ing-unoxlv dized, thus exposing them to the direct action of the free oxygen in the solution. I hesitate to prescribe any time limit'for the operation,

because Ihave found that indeterminate variables of conditionenter into the process. The time required for the hydrogen peroxld methodto produce its full effect is measured .byhour s, as contrasted with weeksin the former-case. R f r The third yariation of method is one which maybe called promoted or provoked. oxida wetting", or, saturating.- or .otherwise inti- I indications are that a the operation is cata- 106 y tion, and. involves PI'GPBJ'MJIOIIC of resin by 7 ,der, spread it so as to. expose as much as pos-.' I

Jmately associating it with a substance which,

Ivhave discovered several substances which operate as promoters of oxidation of resin,

and which, in various degrees, expedite and render uniform the desired oxidation.

' In each case, grind rosin to a powder, and

first saturate it with. a solution of the pro-. moter of oxidation; then dry the prepared are: calcium hypochloritev (bleaching powv .der) formaldeh'yde, dilute sulfuric acid, so lution of s'ulfuludioxid in water, milk of rosin powder,'exposing it to air thoroughly. Substances which I have discovered to be efeotive as promoters of oxidation of resin lime with a small percentage of soda ash, and turpentine. I

The specific method which I believe to yield the best results is as follows:

Melt rosinyadd thereto amixture of 5% turpentine, 1% soda ash, 1 and s1aked lime (these percentages being on the weight of-rosin) vand mix th'oroughlyi-v ,Cool'and then grind the mixture to pass a 60 mesh sieve; expose thecomminuted mass to "air at a temperature about l-10 F. (prefer'ably tumbling or agitating it occasionally) until a sample yields a clear and indefinitely extensible'fluid solution'inan equal weight of water containing ;the requisite" amount of ammonia for 'sapomficati'on. The oxidized-'1 rosin produced the above described variations'on t 'e' fundamental. method win be found capable of forming an ammoniate, indefinitely extensible in water.

I claim t 4 1. The method of modifying rosin, which consists in distributing through it a substance provocative of oxidation, thereafter oxidizing the rosin until'capable of forming an ammoniate indefinitely extensible in water. 2. The method of modifying rosin, which consists in distributing throu h itia mixture of turpentine, soda ash an -slacked lime, thereafter oxidizing the rosin until capable of forming an ammoniate indefinitely extensible in water.

3. The method of modifying rosin, which consists in making a fused* mixture of the rosin with turpentine, soda ash and slaked ash and part slaked lime; cooling and comminuting said mixture, 'and tl1ereaft r exposing it tovoxygen at about 110 .C. unt I it is capable of forming an ammoniate in-' definitely-extensible in water. a

Si ned by me at Boston, Massachusetts, this %fth day of J anuar 1920.

' ,1 i s GEO GE W. MILES. 

